EP3041988B1 - Papier de séparateur pour piles électrochimiques - Google Patents

Papier de séparateur pour piles électrochimiques Download PDF

Info

Publication number
EP3041988B1
EP3041988B1 EP14776593.7A EP14776593A EP3041988B1 EP 3041988 B1 EP3041988 B1 EP 3041988B1 EP 14776593 A EP14776593 A EP 14776593A EP 3041988 B1 EP3041988 B1 EP 3041988B1
Authority
EP
European Patent Office
Prior art keywords
aramid
paper
para
fibril
less
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP14776593.7A
Other languages
German (de)
English (en)
Other versions
EP3041988A1 (fr
Inventor
Fresia Alvarado Chacon
Ramon VAN ROOIJ
Richard Visser
Jan David TIECKEN
Frank DIEDERING
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Teijin Aramid BV
Original Assignee
Teijin Aramid BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Teijin Aramid BV filed Critical Teijin Aramid BV
Priority to EP14776593.7A priority Critical patent/EP3041988B1/fr
Publication of EP3041988A1 publication Critical patent/EP3041988A1/fr
Application granted granted Critical
Publication of EP3041988B1 publication Critical patent/EP3041988B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21G—CALENDERS; ACCESSORIES FOR PAPER-MAKING MACHINES
    • D21G1/00—Calenders; Smoothing apparatus
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10—Organic non-cellulose fibres
    • D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H13/26—Polyamides; Polyimides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/423—Polyamide resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/494—Tensile strength
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
    • D10B2331/021—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides aromatic polyamides, e.g. aramides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/48—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances fibrous materials
    • H01B3/52—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances fibrous materials wood; paper; press board
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention pertains to a paper suitable as separator for electrochemical cells.
  • the invention also pertains to a method for making the separator paper, to the use of the paper in electrochemical cells, and to electrochemical cells provided with a separator paper according to the invention.
  • electrochemical cells comprise a cathode, an anode, and electrolyte, wherein the cathode and anode are separated through the separator, which comprises the electrolyte.
  • the purpose of the separator is on the one hand keeping the electrodes apart to prevent short-circuiting, while on the other hand allowing ionic charge to pass to complete the electrical circuit during the passage of current.
  • the separator should be able to withstand degradation under the conditions prevailing in the cell during use. Additionally, the separator should be as thin as possible to give increased performance, without however compromising on stability. Stability to high temperatures is required to increase cell safety and stability.
  • separators in particular for lithium ion batteries, are often polymer microporous membranes, typically polyolefin membranes based on polyethylene and/or polypropylene.
  • work is being done to develop separators with improved properties.
  • One way forward is the development of non-woven based on aramid.
  • Aramid combines a high strength with high temperature resistance and therefore is an attractive material for many industrial applications. That it can be formulated into thin papers with good properties is an additional reason why it is attractive for separators.
  • US2007/0167101 describes a separator paper comprising aramid staple fiber, fibrillated aramid, and optionally aramid fibrid.
  • US2003/0180622 describes a separator paper which comprises organic fibers fibrillated into a fiber diameter of 1 micron or less, and unfibrillated organic fibers having a fineness of 0.5 dtex or less.
  • EP1737004 describes a separator comprising 15-80 wt.% of fibrillated heat-resistant fiber, 5-35 wt.% of fibrillated cellulose, and 10-75 wt.% of non-fibrillated fiber.
  • the fibrillated heat-resistant fiber preferably is para-aramid.
  • the present invention provides such a paper.
  • the present invention therefore pertains to a paper suitable for use as separator in electrochemical cells, which comprises at least 60 wt.% of aramid fibril and at least 1 wt.% of aramid fiber, the paper having a grammage of 5 to 100 g/m2, and the aramid fibril having a Canadian Standard Freeness (CSF) in the wet phase of less than 300 ml and a specific surface area (SSA) after drying of less than 3 m2/g.
  • CSF Canadian Standard Freeness
  • SSA specific surface area
  • the paper according to the invention comprises at least 60 wt.% of aramid fibril. If the amount of aramid fibril is too low, the properties of the separator paper will be insufficient. In particular the coverage of the paper will be insufficient, pinholes may appear that will lead to insufficient electrical insulation between the cathode and the anode, leading to short circuiting of the electrochemical cell.
  • the maximum of the amount of aramid fibril is determined by the minimum amount of fiber, which will be discussed in more detail below.
  • the paper comprises at most 90 wt.% of aramid fibril, in particular at most 80 wt.% of aramid fibril. An amount of 62-80 wt.% of aramid fibril may be preferred to obtain a separator paper with good properties.
  • the aramid fibril is in particular para-aramid fibril.
  • the fibril in the paper according to the invention has a Canadian Standard Freeness (CSF) of less than 300 ml.
  • CSF is a parameter often used in the art of pulp and paper technology. It is a measure of the drainability of a pulp suspension in water. CSF can be determined in accordance with TAPPI T227. It may be preferred for the fibril used in the present invention to have a CSF of less than 200 ml, more specifically less than 150 ml.
  • the lower limit for the CSF is not critical to the present invention. As a general value, a lower limit of 1 ml may be mentioned.
  • the aramid fibril used in the present invention has a specific surface area (SSA) after drying of at most 3 m2/g.
  • SSA specific surface area
  • the lower limit for the surface area after drying is not critical to the present invention. As a general value, a lower limit of at least 0.1 m2/g may be mentioned.
  • Specific surface area can determined using adsorption of nitrogen by the BET specific surface area method, using a Gemini 2375 manufactured by Micromeretics, with the fibrils being dried at 120 °C overnight, followed by flushing with nitrogen for at least 1 h at 200 °C.
  • the aramid fibril used according to the invention may have a weight weighted length for particles having a length above 250 micron (WL0.25) of less than 1.2 mm.
  • This parameter means that of the particles having a length above 250 microns, the weight weighted average length of the particles is below 1.2 mm. This is again a measure for the fineness of the fibril. It may be preferred for the fibril to have a WL0.25 of less than 1.0 mm. As a minimum, a value of 250 microns may be mentioned.
  • Fibril length measurement can be done using the Pulp ExpertT"'FS (ex Metso). As length the average length (AL), the length weighted length (LL), weight weighted length (WL) is used.
  • aramid pulp is obtained by subjecting aramid fibers to one or more refining or fibrillating steps, which results in fibrillated pulp, comprising a fiber stem to which fibrils are attached.
  • the surface area increases when the pulp is further refined to obtain smaller fibrils, with a CSF of less than 300 ml. Therefore, the fibrils used in the present invention, which have a relatively low surface area after drying are generally not obtained by fibrillating fibers, as the material obtained by this process will generally not have the claimed combination of properties.
  • Aramid fibril suitable for use in the present invention is described, e.g., in WO2005/059211 to Teijin Twaron , and can be obtained by the methods described therein. In this method, the fibrils are obtained directly from a polymer solution.
  • the fibrils obtained by the process of this reference are subjected to shear forces, e.g., refining. Refining can be carried out to further decrease surface area after drying and the CSF.
  • the aramid fibril used in the present invention in particular para-aramid fibril, may be obtained by a process comprising the steps of polymerizing an aromatic diamine and an aromatic dicarboxylic acid halide to an aramid polymer, in a mixture of N-methylpyrrolidone or dimethylacetamide and calcium chloride or lithium chloride, to obtain a dope wherein the polymer is dissolved in the mixture and the polymer concentration is 2 to 6 wt. %, converting the dope to fibrils by using a jet spin nozzle under a gas stream, and coagulating the fibrils using a coagulation jet.
  • the hydrochloric acid formed during the polymerisation reaction is neutralized to obtain a neutralized dope.
  • the (relative viscosity) of the aramid polymer is between 2.0 and 5.0.
  • the fibrils obtained by the process described above are subjected to shear forces, e.g., refining before they are incorporated into the paper of the invention.
  • the paper according to the invention comprises at least 1 wt.% of aramid fiber, more specifically at least 5 wt.%, in particular at least 10 wt.%.
  • the amount of aramid fiber is at most 40 wt.%, in particular at most 38 wt.%, still more in particular at most 30 wt%.
  • the aramid fiber can be meta-aramid, meta-para-aramid, or para-aramid.
  • the use of meta-para-aramid or para-aramid fiber is considered preferred, because it will lead to a paper with good dimensional stability.
  • the use of para-aramid fiber is considered particularly preferred.
  • the combination of para-aramid fibril with para-aramid fibers delivers a separator that can withstand high temperatures during the cell making process. By using para-aramid the pore structure is not changed when subjected to high temperatures. Dimensional stability at high temperature and during electrolyte uptake make the material suitable in cell assembling and cell function.
  • the aramid fiber refers to aramid fibres cut to a number-average length which generally is in the range of 2-15 mm, in particular a length of 2-10 mm, more in particular 3-8 mm, more in particular 6 mm.
  • the linear density is preferably less than 1.6 dtex, preferably less than 1.3 dtex, more in particular a linear density of less than 0.8 dtex. It has been found that a decrease in linear density leads to improved properties, in particular increased starting point of discharge capacity.
  • separator paper according to the invention may be present in the separator paper according to the invention, as long as their presence fits in with the weight percentages of aramid fibril and aramid fiber.
  • the paper comprises at least 70 wt.% of the total of meta-para aramid and para-aramid, in particular at least 80 wt.%, more in particular at least 90 wt.%, still more in particular at least 95 wt.%, even more in particular at least 98 wt.%.
  • the paper of the invention may comprise at least 60 wt.% of para-aramid, in particular at least 70 wt.% of para-aramid, more in particular at least 80 wt.%, still more in particular at least 90 wt.%, even more in particular at least 95 wt.%, or even at least 98 wt.%.
  • aramid refers to an aromatic polyamide which is a condensation polymer of aromatic diamine and aromatic dicarboxylic acid halide. Aramids may exist in the meta-form, the para-form, and the meta-para form.
  • a meta-aramid is defined as an aramid wherein at least 85% of the bonds between the aromatic moieties are meta-aramid bonds.
  • a para-aramid is defined as an aramid wherein at least 85% of the bonds between the aromatic moieties are para-aramid bonds.
  • a meta-para-aramid is defined as an aramid wherein at least 16% of the bonds between the aromatic moieties are meta-aramid bonds and at least 16% of the bonds between the aromatic moieties are para-aramid bonds.
  • meta-para aramid i.e., a copolymer having meta- and para-bonds is copolyparaphenylene/3,4'-oxy-diphenylene terephthalamide (Technora®) which contains about 33% meta-bonds. It is preferred for the para-aramid used in the present invention to have at least 90%, more in particular at least 95%, of the bonds between the aromatic moieties in the form of para-aramid bonds.
  • para-aramid examples may be mentioned poly(paraphenylene terephthalamide), poly(4,4'-benzanilide terephthalamide), poly(paraphenylene-4,4'-biphenylenedicarboxylic acid amide) and poly(paraphenylene-2,6-naphthalenedicarboxylic acid amide).
  • poly(para-phenylene terephthalamide), also indicated as PPTA, is particularly preferred.
  • the paper can comprise one or more common papermaking components, such as fillers including mica, clay such as kaolin and bentonite, minerals, binders, fibers, tackifiers, adhesives, and the like.
  • the fillers such as kaolin
  • the fillers may be introduced into the paper by way of aramid fibril and/or aramid fibrid, e.g., by using filler-containing fibrils or fibrids manufactured by incorporating filler into the fibril or fibrid during the manufacturing process, for instance as has been described in WO 2008/122374 .
  • such components may be present in an amount not exceeding 25 wt.%. If these components are used, they are generally present in an amount of 2-25 wt.%. Depending on the compound, a range of 10-25 wt.% may be mentioned.
  • papers containing less than 2 wt.% of additional components, or substantially no additional components are also clearly envisaged.
  • the paper according to the invention has a grammage of 5 to most 100 g/m2, more specifically between 5 and 50 g/m2.
  • the grammage should be as low as possible as can be achieved without detrimentally affecting the further properties of the separator paper, e.g., between 5 and 30 g/m2.
  • the separator paper has a grammage of 10 to 25 g/m2.
  • the paper according to the invention has a thickness of at most 250 micron, preferably below 100 micron, most preferably below 40 micron. A minimum value of 5 micron may be mentioned.
  • the paper according to the invention has a Gurley of less than 200 seconds, more preferably less than 50 seconds. Gurley is a measure for the air permeability of the paper. It can be determined in accordance with TAPPI T460. It may be preferred for the Gurley to be less than 10 seconds.
  • the paper according to the invention has an average pore size or mean flow pore size of less than 12 micron.
  • the average pore size should not be too high, as this will increase the risk of short-circuiting.
  • the average pore size is measured via capillary flow porometry. Capillary flow porometry is based on the displacement of a wetting liquid inside a porous network by means of an inert gas flow. By using the measured wet and dry curve, the mean flow pore size is calculated in accordance with ASTM F 316-03. It may be preferred for the average pore size to be less than 10 micron.
  • Mean flow pore sizes smaller than 100 nm are usually accompanied by high Gurley values which might make the paper unsuitable for the application. Therefore, the mean flow pore size preferably is between 0.1 and 10 micron.
  • the paper of the present invention typically has a tensile strength of at least 2 N/cm, in particular at least 4 N/cm, more in particular at least 5 N/cm. Tensile strength can be determined in accordance with ISO1924-2. If the tensile strength of the paper is insufficient, processing it into an electrochemical cell will be difficult.
  • the paper of the present invention has a tear resistance of at least 60 mN. The tear resistance is a measure of how well a material can withstand the effect of tearing when an initial cut is present. This is a measure of the susceptibility of the paper to damage propagation. The tear resistance can be determined in accordance with ISO1974. It is preferred for the tear resistance to be at least 100 mN, in particular at least 130 mN.
  • the paper according to the invention may be manufactured by paper making methods known in the art.
  • the papers are manufactured by the following process.
  • a suspension generally an aqueous suspension, is prepared comprising the aramid fibril, aramid fiber, and optionally further components as described above.
  • the suspension is applied onto a porous screen, so as to lay down a mat of randomly interwoven material onto the screen. Water is removed from this mat, e.g., by pressing and/or applying vacuum, followed by drying to make paper.
  • a calendaring step may be applied to increase the density of the paper.
  • Calendering steps are known in the art. They generally involve passing the paper through a set of rolls, if so desired at increased temperature.
  • the present invention also pertains to the use of the paper above as separator in electrochemical cells.
  • electrochemical cells wherein the paper according to the invention may be used are batteries, fuel cells, and supercapacitors.
  • Use of the paper according to the invention in secondary batteries, specifically lithium ion batteries is particularly preferred, as this type of battery has been found to benefit in particular from the properties of the separator paper according to the invention.
  • the invention also pertains to an electrochemical cell comprising a cathode, an anode, and an electrolyte between the cathode and the anode, wherein the cathode and the anode are separated by a separator paper according to the invention.
  • the invention also pertains to an electrochemical cell which is a lithium ion battery comprising a cathode, an anode, and an electrolyte between the cathode and the anode, wherein the electrolyte comprises lithium salts, the cathode and the anode being separated by a separator paper according to the invention.
  • Lithium ion batteries are known in the art and require no further elucidation here.
  • the anode generally comprises carbon, e.g., in the form of graphite.
  • the cathode generally comprises a (mixed) metal oxide or (mixed) metal phosphate, e.g.
  • the electrolytes are mostly nonaqueous solutions, e.g., comprising lithium salts dissolved in aprotic organic solvents, e.g. a mixture of carbonate solvents selected from cyclic carbonates (for example ethylene carbonate or propylene carbonate) and linear carbonates (dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate).
  • aprotic organic solvents e.g. a mixture of carbonate solvents selected from cyclic carbonates (for example ethylene carbonate or propylene carbonate) and linear carbonates (dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate).
  • An aramid paper was manufactured from para-aramid fibrils and para-aramid fibers.
  • the para-aramid fibrils had a Canadian Standard Freeness of 120 ml, a specific surface area after drying of 0.86 m2/g and a weight weighted length for particles having a length > 250 micron of 0.93 mm.
  • the fibrils were manufactured as described in WO2005/059211 , with a further shear step being carried out before incorporating them into the paper.
  • the para-aramid fibers were para-aramid shortcut with a length of 6 mm and a linear density of 1.1 dtex.
  • the paper contained 70 wt.% para-aramid fibrils and 30 wt.% para-aramid fiber.
  • the paper had the following properties:
  • the paper was subjected to cycle testing in an electrochemical cell in accordance with the procedure described below.
  • Celgard 2325 standard commercially available polyolefin material
  • Separator papers were tested in pouch cells with a maximum capacity of 80 mAh.
  • Commercial NMC cathode and a graphite anode were used.
  • Electrolyte used was 1 M LiPF6 in EC:EMC (3:7%wt), 2%wt VC was used as additive.
  • the paper according to the invention shows a much higher capacity retention than the commercially available product. After 900 cycles cells containing Celgard separator have reached the end of life (80% capacity) whilst cells containing aramid separator still show 97% capacity retention. This means that an electrochemical cell comprising the paper according to the invention will have a longer lifetime than an electrochemical cell comprising the comparative product.
  • comparative papers were manufactured with equivalent compositions, grammage (19 g/m2), thickness (30 microns), and density (0.6 g/cc) as the paper according to the invention, but wherein fibrils with different properties were used. All papers were manufactured on a Rapid Koethe (RK) handsheet former according to the method of ISO 5269-2.
  • RK Rapid Koethe
  • Table 2 Recipe % Fibrils % Highly refined pulp %Refined pulp Fibers Invention 70 30 CE1 70 30 CE2 70 30
  • para-aramid fibrils were used with a specific surface area after drying of 0.42 m2/g, a Canadian Standard Freeness of 50 ml, and a weight weighted length for particles having a length > 250 micron of 0.70 mm.
  • This material was obtained by jet-spinning polymer solution as described in WO2005/059211 , followed by a further shear process step.
  • highly refined para-aramid pulp was used, with a specific surface area after drying of 14 m2/g, a Canadian Standard Freeness of 90 ml, and a weight weighted length for particles having a length > 250 micron of 0.84 mm. This pulp was obtained by subjecting fibers to a number of high shear refining steps.
  • Tensile strength (TS) was determined in accordance with ISO 1924-2.
  • the paper according to the invention shows a tensile strength retention after wet aging which is much higher than the tensile strength retention of the comparative papers. This means that the paper according to the invention will show less degradation during use, leading to an electrochemical cell with a longer lifetime. Additionally, the absolute value of the strength after aging of the paper according to the invention is also higher than the strength after aging of the comparative papers, which is an additional advantage. The same goes for the dry strength.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Paper (AREA)
  • Cell Separators (AREA)
  • Secondary Cells (AREA)

Claims (15)

  1. Papier utilisable comme séparateur dans une pile électrochimique, qui comprend au moins 60 % en poids de fibrille d'aramide et au moins 1 % en poids de fibre d'aramide, ce papier présentant un grammage de 5 à 100 g/m2, et la fibrille d'aramide présentant un indice d'égouttage CSF (Canadian Standard Freeness) en phase humide inférieur à 300 ml et une surface spécifique (SSA) après séchage inférieure à 3 m2/g.
  2. Papier selon la revendication 1, qui comprend au plus 90 % en poids de fibrille d'aramide, en particulier au plus 80 % en poids de fibrille d'aramide, et plus particulièrement entre 62 et 80 % en poids de fibrille d'aramide, la fibrille étant en particulier de la fibrille de para-aramide.
  3. Papier selon la revendication 1 ou 2, dans lequel la fibrille d'aramide présente un indice d'égouttage CSF en phase humide inférieur à 200 ml, en particulier inférieur à 150 ml, et/ou une surface après séchage inférieure à 1,5 m2/g.
  4. Papier selon l'une quelconque des revendications précédentes, dans lequel la fibrille d'aramide présente une longueur pondérée en poids inférieure à 1,2 mm pour les particules d'une longueur supérieure à 250 µm (WL 0,25).
  5. Papier selon l'une quelconque des revendications précédentes, dans lequel la proportion de fibre d'aramide représente au moins 5 % en poids, en particulier au moins 10% en poids, et/ou au plus 38 % en poids, plus particulièrement au plus 30 % en poids, la fibre étant de préférence de la fibre de méta-para-aramide ou de para-aramide, et plus particulièrement de la fibre de para-aramide.
  6. Papier selon l'une quelconque des revendications précédentes, dans lequel la fibre d'aramide présente une longueur moyenne en nombre comprise dans l'intervalle allant de 2 à 15 mm, en particulier de 2 à 10 mm, plus particulièrement de 3 à 8 mm, et encore plus particulièrement une longueur de 6 mm, et/ou dans lequel la fibre d'aramide présente une masse linéique inférieure à 1,6 dtex, de préférence inférieure à 1,3 dtex, et mieux encore inférieure à 0,8 dtex.
  7. Papier selon l'une quelconque des revendications précédentes, dans lequel la proportion totale combinée de méta-para-aramide et de para-aramide représente au moins 70 % en poids, en particulier au moins 80 % en poids, plus particulièrement au moins 90 % en poids, encore plus particulièrement au moins 95 % en poids et plus particulièrement encore au moins 98 % en poids, et/ou la proportion de para-aramide représente au moins 60 % en poids, en particulier au moins 70 % en poids, plus particulièrement au moins 80 % en poids, encore plus particulièrement au moins 90 % en poids, et plus particulièrement encore au moins 95 % en poids, voire au moins 98 % en poids.
  8. Papier selon l'une quelconque des revendications précédentes, qui présente un grammage valant de 5 à 50 g/m2, en particulier 5 à 30 g/m2, et plus particulièrement 10 à 25 g/m2.
  9. Procédé de fabrication d'un papier selon l'une quelconque des revendications précédentes, dans lequel on prépare une suspension comprenant de la fibrille d'aramide, de la fibre d'aramide et, en option, d'autres constituants, on applique cette suspension sur une toile poreuse de manière à déposer sur la toile un mat de matière à entrelacement aléatoire, on élimine l'eau de ce mat, puis on fait sécher le mat en vue de former un papier que l'on soumet, en option, à une étape de calandrage.
  10. Procédé selon la revendication 9, qui comprend en outre une étape de fabrication de fibrille d'aramide au moyen d'un procédé comportant les étapes suivantes :
    - polymérisation d'une diamine aromatique et d'un halogénure d'acide dicarboxylique aromatique en un polymère d'aramide, dans un mélange de N-méthylpyrrolidone ou de diméthylacétamide et de chlorure de calcium ou de chlorure de lithium, en vue d'obtenir une solution à filer dans laquelle le polymère est dissous au sein du mélange et se trouve à une concentration de 2 à 6 % en poids,
    - transformation de la solution à filer en fibrilles au moyen d'une buse de filature à jet sous un courant de gaz,
    - coagulation des fibrilles au moyen d'un jet de coagulation,
    - et, en option, exposition des fibrilles à des forces de cisaillement.
  11. Utilisation d'un papier selon d'une quelconque des revendication 1 à 8 précédentes, en tant que séparateur dans une pile électrochimique.
  12. Utilisation selon la revendication 11, dans laquelle la pile électrochimique est une batterie au lithium-ion.
  13. Pile électrochimique comprenant une cathode, une anode et un électrolyte entre la cathode et l'anode, dans laquelle la cathode et l'anode sont séparées par un papier séparateur selon l'une quelconque des revendications 1 à 8.
  14. Pile électrochimique selon la revendication 13, qui est une batterie au lithium-ion, dans laquelle l'électrolyte comprend des ions lithium.
  15. Batterie au lithium-ion selon la revendication 14, dans laquelle l'anode comprend du carbone, la cathode comprend un oxyde de métal ou oxyde mixte de métaux, ou un phosphate de métal ou phosphate mixte de métaux, et l'électrolyte comprend un complexe de lithium au sein d'un solvant organique.
EP14776593.7A 2013-09-06 2014-08-28 Papier de séparateur pour piles électrochimiques Active EP3041988B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP14776593.7A EP3041988B1 (fr) 2013-09-06 2014-08-28 Papier de séparateur pour piles électrochimiques

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP13183313 2013-09-06
PCT/EP2014/068227 WO2015032678A1 (fr) 2013-09-06 2014-08-28 Papier de séparation pour cellules électrochimiques
EP14776593.7A EP3041988B1 (fr) 2013-09-06 2014-08-28 Papier de séparateur pour piles électrochimiques

Publications (2)

Publication Number Publication Date
EP3041988A1 EP3041988A1 (fr) 2016-07-13
EP3041988B1 true EP3041988B1 (fr) 2017-07-19

Family

ID=49117734

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14776593.7A Active EP3041988B1 (fr) 2013-09-06 2014-08-28 Papier de séparateur pour piles électrochimiques

Country Status (6)

Country Link
US (1) US10003057B2 (fr)
EP (1) EP3041988B1 (fr)
JP (1) JP6449888B2 (fr)
KR (1) KR102218165B1 (fr)
CN (1) CN105723030B (fr)
WO (1) WO2015032678A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6649701B2 (ja) * 2015-05-28 2020-02-19 デュポン帝人アドバンスドペーパー株式会社 アラミド紙、及びその製造方法
EP3548657B1 (fr) * 2016-11-30 2022-08-17 Teijin Aramid B.V. Papier aramide approprié à être utilisé dans des applications électroniques
CN107452921B (zh) * 2017-07-20 2019-06-18 清华大学 一种对位芳纶纳米纤维复合锂离子电池隔膜的制备方法
CN107652430A (zh) * 2017-09-07 2018-02-02 烟台泰和新材料股份有限公司 一种锂离子电池正负极隔膜用改性对位芳纶聚合物原液的生产方法
WO2019228972A1 (fr) 2018-05-28 2019-12-05 Teijin Aramid B.V. Papier à base d'aramide ayant des propriétés améliorées
US11078627B2 (en) 2018-08-14 2021-08-03 Dupont Safety & Construction, Inc. High tensile strength paper suitable for use in electrochemical cells
US11271136B2 (en) * 2018-11-07 2022-03-08 Seoul Viosys Co., Ltd Light emitting device
US11509016B2 (en) * 2019-03-15 2022-11-22 Dupont Safety & Construction, Inc. Papers useful as thermal insulation and flame barriers for battery cells
WO2023059989A1 (fr) * 2021-10-07 2023-04-13 Dupont Safety & Construction, Inc. Matériau en feuille non tissé comprenant un substrat et revêtement de fibrilles appliqué
CN114922002A (zh) * 2022-04-13 2022-08-19 株洲时代新材料科技股份有限公司 一种耐压电容器纸及其制备方法

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5263268A (en) * 1975-10-23 1977-05-25 Unitika Ltd Method of manufacture of formed product of aromatic polyamide
JP3777711B2 (ja) 1997-04-15 2006-05-24 王子製紙株式会社 薄葉多孔紙
US6905798B2 (en) * 2000-05-29 2005-06-14 Mitsubishi Paper Mills Limited Separator for electrochemical device and method for producing the same
MXPA05011957A (es) 2003-05-08 2006-02-02 Teijin Twaron Bv Solucion polimerica no fibrosa de para-aramida con viscosidad relativa alta.
MY138441A (en) * 2003-12-09 2009-06-30 Teijin Aramid Bv Aramid fibrils
JP2005307360A (ja) * 2004-04-16 2005-11-04 Du Pont Teijin Advanced Paper Kk アラミド薄葉材およびそれを用いた電気電子部品
JP4377911B2 (ja) 2004-04-16 2009-12-02 三菱製紙株式会社 電気化学素子用セパレータ
JP4648841B2 (ja) * 2005-02-01 2011-03-09 三菱製紙株式会社 電子部品用セパレータ
US20090101295A1 (en) * 2005-12-21 2009-04-23 Merriman Edmund A Self-Bonding Polypridobismidazole Pulp and a Process for Making Same
RU2458191C2 (ru) 2007-04-05 2012-08-10 Тейджин Арамид Б.В. Частицы, состоящие из композиционного материала пара-арамида и дополнительного материала
JP5529148B2 (ja) * 2009-09-16 2014-06-25 株式会社クラレ 非水系電池用セパレータ及びそれを用いた非水系電池、ならびに非水系電池用セパレータの製造方法
CN101872852B (zh) * 2010-06-21 2012-09-26 深圳昊天龙邦复合材料有限公司 基于芳纶纤维的电池隔膜的制备方法
US9666848B2 (en) 2011-05-20 2017-05-30 Dreamweaver International, Inc. Single-layer lithium ion battery separator
US20140141337A1 (en) * 2012-11-20 2014-05-22 Brian G. Morin Versatile Single-Layer Lithium Ion Battery Separators Having Nanofiber and Microfiber Components

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
JP2016535416A (ja) 2016-11-10
US20160197325A1 (en) 2016-07-07
KR20160054550A (ko) 2016-05-16
KR102218165B1 (ko) 2021-02-24
US10003057B2 (en) 2018-06-19
CN105723030B (zh) 2018-06-05
JP6449888B2 (ja) 2019-01-09
WO2015032678A1 (fr) 2015-03-12
EP3041988A1 (fr) 2016-07-13
CN105723030A (zh) 2016-06-29

Similar Documents

Publication Publication Date Title
EP3041988B1 (fr) Papier de séparateur pour piles électrochimiques
US9614249B2 (en) Separator for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery
EP2169743B1 (fr) Séparateur pour batterie secondaire non aqueuse, son procédé de production et batterie secondaire non aqueuse
EP3281241B1 (fr) Séparateurs de batterie comprenant des particules inorganiques
JP5706214B2 (ja) セパレータ
JP6100250B2 (ja) 非水系電池用セパレータ及び非水系電池
JP5551525B2 (ja) 極細径不織布からなるセパレータ
WO2013054884A1 (fr) Membrane microporeuse et son procédé de fabrication
WO2013054889A1 (fr) Membrane microporeuse et son procédé de production
WO2017150439A1 (fr) Séparateur de batterie alcaline et batterie alcaline
KR20070047772A (ko) 세퍼레이터 및 그것을 이용한 전기 전자 부품
US20220158299A1 (en) Lithium ion battery separator and lithium ion battery
CN104518189A (zh) 非水电解质二次电池用隔板和非水电解质二次电池
JP2010238640A (ja) 蓄電デバイス用セパレータ
JP2016182817A (ja) 積層体
WO2020235508A1 (fr) Séparateur pour batterie secondaire non aqueuse, son procédé de fabrication et batterie secondaire non aqueuse
JP2007242584A (ja) 電子部品用セパレータ
JP2011258463A (ja) 非水系電気電子部品用セパレータ
JP2022102452A (ja) リチウムイオン二次電池用セパレータ及びリチウムイオン二次電池
US20230207970A1 (en) Separator for non-aqueous secondary battery and non-aqueous secondary battery
JP2019207775A (ja) リチウムイオン電池セパレータ及びリチウムイオン電池
JP2019212492A (ja) リチウムイオン電池セパレータ及びリチウムイオン電池
JP2019212491A (ja) リチウムイオン電池セパレータ及びリチウムイオン電池

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20160406

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20170302

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 910509

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170815

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 4

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602014012071

Country of ref document: DE

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 910509

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170719

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171019

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170719

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170719

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170719

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170719

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170719

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171019

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171020

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170719

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170719

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170719

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171119

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170719

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602014012071

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170831

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170831

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170719

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170719

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170719

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170719

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170719

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170719

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170719

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170719

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20170831

26N No opposition filed

Effective date: 20180420

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170828

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170828

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170719

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170828

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20140828

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170719

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170719

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170719

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170719

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170719

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230710

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20230824

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20230824

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230824

Year of fee payment: 10

Ref country code: DE

Payment date: 20230831

Year of fee payment: 10